Solidification retardation of liquid crystalline compositions with steroid derivatives of isostearyl carbonate

ABSTRACT

Solidification of liquid crystalline compositions is retarded by incorporating therein compounds which are steroid derivatives of isostearyl carbonate. These novel carbonates which are quite stable to environmental factors such as ultraviolet light exposure, temperature changes, oxidation, etc., retard solidification of liquid crystalline compositions for extended periods of time. Moreover, these compounds, some of which of themselves exhibit color play, can be used in increasing amounts to increasingly narrow the color play range without noticeably decreasing the specular intensity of the color changes of liquid crystalline compositions.

{22] Filed:

United States Patent [191 Brown, Jr. et al.

[ Nov. 18, 1975 SOLIDIFICATION RETARDATION OF LIQUID CRYSTALLINE COMPOSITIONS WITH STEROID DERIVATIVES OF ISOSTEARYL CARBONATE [75] Inventors: George T. Brown, Jr., Dayton;

' Donald B. Clark, Kettering; Donald E. Koopman, Miami Township, all of Ohio [73] Assignee: Djinnii Industries, Inc., Dayton,

Ohio

.Aug. 26, 1974 [21] Appl. No.: 500,671

[52] C1. 252/299; 23/230 LC; 73/356; 116/114 V; 161/410; 252/408 LC; 252/352; 260/379.4;260/379.45; 260/4105; 350/160 LC [51] Int. Cl. C09K 3/34; CO7C 97/24; C0913 1/50 [58] Field of Search 252/299, 408 LC, 352; 23/230 LC; 350/160 LC; 73/256; 161/410;

[56] References Cited UNITED STATES PATENTS 3,578,844 5/1971 Churchill et a1, 252/299 3,580,864 5/1971 Goldberg et al. 252/299 3,580,865 5/1971 Goldberg 252/299 3,585,381 6/1971 Hodson et a1 252/299 3,619,254 ll/l97l Davis 252/299 3,620,889 1 1/1971 Baltzer 252/299 3,633,425 1/1972 Sanford 252/299 3,647,279 3/1972 Sharpless et all 252/299 3,656,909 4/1972 Dixon et al. 252/299 3,697,297 10/1972 Churchill et al. 252/299 3,720,623 3/1973 Cartmell et al. 252/299 OTHER PUBLICATIONS Elser, Wolfgang et al., Mol. Cryst. Liq. Cryst., Vol. 20, No. 1, pp. 77-86 (1973).

Gray, G. W. and Winsor, P. A., Liquid Crystals & Plastic Crystals, Vol. 1, Ellis Horwood Ltd., London, pp. 142-147 (1974).

Primary Examiner-Benjamin R. Padgett Assistant Examiner-T. S. Gron range without noticeably decreasing the specular intensity of the color changes of liquid crystalline compositions.

7 Claims, No Drawings SOLIDIFICATION RETARDATION OF LIQUID CRYSTALLINE COMPOSITIONS WITH STEROID DERIVATIVES OF ISOSTEARYL CARBONATE BACKGROUND OF THE INVENTION 1. Field of the invention This invention relates to a novel group of chemical compounds which are steroid derivatives of isostearyl carbonate, to the use thereof as solidification retarders in liquid crystalline compositions, to the solidification retarded compositions, to the manufactured articles made therefrom.

2. Description of the prior art Liquid crystals may be defined as that class of matter which has an intermediate or mesmorphic state in which these substances behave mechanically as liquids yet exhibit many optical properties of crystals. The mesomorphic state or liquid crystalline phase is obtained either by heating liquid crystals that are in the solid phase or by cooling liquid crystals that are in the liquid phase. Liquid crystal substances have been classified as belonging in one of three different types, viz., cholesteric, nematic and smectic. The cholesteric structure is distinguished from the nematic and smectic structures by its markedly different optical properties, for example, cholesteric materials are optically negative whereas nematic and smectic materials are optically positive.

Thin films of cholesteric liquid crystals upon interaction with light exhibit a property, termed selective scattering, whereby light rays impinging upon the film may leave at an angle unrelated to the angle of incident light. The color and intensity of the scattered light depends upon the temperature of the scattering material and upon the angle of incident illumination. The range of temperatures within which visible colors are displayed as a result of scattering of white light from cholesteric liquid crystals is known as the color play range. A color play range may be made as wide as 30 C. or more (for example, start of red at 37 C. through the visible color spectrum with start of blue at 67 C.) or may be as narrow as l C. (for example, start of red at 30C. through the visible color spectrum with start of blue at 31 C.).

Many liquid crystalline materials having once been -melted, tend to solidify in a short period of time. US.

Pat. No. 3,580,864 describes the use of a compound, cholesteryl erucyl carbonate, to stabilize cholestericphase liquid-crystal compositions against true-solid formation. However, perhaps because of the erucyl carbon-carbon double bond, this compound is not as able to resist ultraviolet light degradation as are the novel compounds of this invention.

The production of steroid alkyl carbonates is well known to persons skilled in the art of steroid synthesis. By way of example one method. but not necessarily the preferred, involves the reaction of alkyl chloroformate (either as a reagent or synthesized in situ by the reaction of phosgene with an alkanol) with pyridine and a sterol. Insoluble pyridine hydrochloride which is precipitated is filtered from the reaction mixture. The oily alkyl steroid carbonate layer is separated from the filtratc by means of a separatory funnel and repeatedly washed with methanol.

BRIEF SUMMARY OF THE INVENTION Many liquid crystalline compositions after a period of time varying from hours to Weeks become unstable and solidify as crystals. The addition of certain steriod derivatives of isostearyl carbonate retards this solidification process and thereby extends the mesomorphic life of these compositions. These solidification retardants are effective at low temperatures as well as at elevated and room temperatures.

SYNTHESIS DESCRIPTION OF STEROID DERIVATIVES OF ISOSTEARYL CARBONATE Steroids are a family of compounds which contain the perhydro-1,2-cyclopentanophenanthren ring system. Asteroid group of C21-Cz9 secondary alcohols of animal or plant origin differs from common alcohols in that they are crystalline solids of melting points in the range of l00200 C.. Cholesterol, a C I-I OH monounsaturated sterol, is found only in the animal world as is cholestanol, a companion compound, which is the product of cholesterol hydrogenation.

Although cholesterol is not found in the plant world, a number of closely related sterols, known as phytosterols, are encountered. For example, stigmasterol, C H OH, is a phytosterol found as a component of a sterol mixture from soybean oil. The nonsaponifiable fraction from soybean oil contains 12-25% of stigmasterol and the remainder is a mixture of sitosterols, C H OH, which are largely monounsaturated carbon 5 carbon 6 stenols.

Cholesterol, stigmasterol and sitosterol are typical members of a group of sterols comprisng a cyclopentenophenanthrene system. The structure and numbering of cyclopentenophenanthrene is (Fieser, L. F. 8!. Fieser, M. Steroids. N.Y., Rheinhold, 1959, p. 1., 346-348.). The following synthesis of cholesteryl isostearyl carbonate is a description of a typical synthesis of a steroid isostearyl carbonate. The steroid is derived from a group of sterols comprising cholesterol, stigmasterol and sitosterol; the halosterols of cholesterol, stigmasterol and sitosterol; and the group of sterols in which the carbon 5 carbon 6 unsaturated bond of cholesterol, stigmasterol and sitosterol is saturated.

Cholesteryl isostearyl carbonate can be synthesized either by the chemical reaction of isostearyl alcohol with cholesteryl chloroformate or by the chemical reaction of isostearyl chloroformate with cholesterol. Cholesteryl chloroformate is available as a reagent or can be synthesized by slowly bubbling phosgene gas through a solution of cholesterol dissolved in anhydrous ethyl ether. This is illustrated by the following chemical reaction:

C,-,H,,,OH COCL, C ,H,,,OCCl HCI Choles- Phosgene Cholesteryl Hydrogen terol chloroformate chloride Cholesteryl chloroformate is chemically reacted with isostearyl alcohol and pyridine to yield cholesteryl isostearyl carbonate and pyridine hydrochloride. The pyridine hydroachloride precipitates out of the benzene solution and is separated from the cholesteryl isostearyl carbonate by means of filtration. The cholesteryl isostearyl carbonate is then isolated from the filtrate. This is illustrated by the following chemical reaction:

lsos'bearyl alcohol* Pyridine hydrochlori do Oil 3 cholesteryl isostearyl carbonate *lsostearyl alcohol is sold as ADOL66 by Ashland Chemical Company. Columbus, Ohio, U.S.A.

The laboratory synthesis of cholesteryl isostearyl carbonate was performed in a three-neck pyrex reaction flask with ground glass joints to which was fitted an additon funnel, a reflux condenser, and a stirrer. The flask was heated by means of a voltage controlled heating mantle. Into the flask 336.9 grams (0.75 mol) of cholesteryl chloroformate were added to 500 milliliters of benzene and heated until the cholesteryl chloroformate dissolved into solution. In a separate flask 205.5 grams (0.76 mol) of isostearyl alcohol were dissolved into 300 milliliters of benzene by the application of heat. The isostearyl alcohol solution was then added to the solution of cholesteryl chloroformate.

Through the use of an addition funnel 60.7 milliliters (0.75 mol) of pyridine dissolved in 100 milliliters of 4 benzene were added dropwise to the contents of the flask. An exothermic reaction followed resulting in the formation of a white solid consisting of pyridine hydrochloride. After complete addition of pyridine, the contents of the flask were refluxed for 1.5 hours at a temperature of about C..

The pyridine hydrochloride was removed by vacuum filtration, using a Buchner funnel and then methanol was added with agitation to the filtrate solution of cholesteryl isostearyl carbonate and benzene. An oily product, cholesteryl isostearyl carbonate which was phased out of solution, was separated from the methanol-benzene phase by means of a separatory funnel. The consistency of the resultant cholesteryl isostearyl carbonate changes from an oil to grease as the temperature is lowered, but even after prolonged storage at pyridine Chole sce ryl chloroformate low temperatures the product did not solidify into a true solid. When used by itself the compound has a color-play range of about 235 C. to 24.0 C..

DESCRIPTION OF THE PREFERRED EMBODIMENTS Steroid derivatives of isostearyl carbonate are used by incorporating them, in amounts up to in liquid crystalline compositions. Reference may be made to US. Pat. No. 3,620,889, lines 16-42, column 5 for a comprehensive (but by no means complete) list of compounds suitable for use in making such compositions. The preferable use of these carbonates is 10 to 80 weight per cent of the liquid crystalline composition; however they are effective when used in amounts as low as 5 weight per cent or less, and they can be used in amounts approaching 100 weight per cent of liquid crystalline compositions.

The following examples are illustrative of the process and products of the present invention and are not to be construed as limiting.

EXAMPLE I To compositions of equal parts of cholesteryl pelargonate (CP) and cholesteryl oleyl carbonate (COC) was added cholesteryl isostearyl carbonate (CIC) in quantitative increments up to about 40 weight per cent. These compositions were melted together and coated onto a black coated temperature probe to a thickness of about one to four thousandths of an inch. Color wasread perpendicular to the surface with the light also normal to the surface of the liquid crystalline films.

Table I presents examples that illustrate the use of CIC with CP and COC, typical liquid crystalline materials, and the effect of the event temperature and the color play temperature range.

Table l Wt. "/1 CIC Wt. 7(- CP Wt. /z COC Temp. (C.) Start Of Red Blue The addition of CIC depressed the onset of the color event temperatures of both the red and blue end of the spectrum, and at the same time, as more CIC was added, especially with additions exceeding 10 per cent by weight, the entire spectrum from red to blue or the color play range was narrowed. In all these compositions the intensity of the spectrum as displayed to the eye did not appreciably vary.

EXAMPLE II To compositions of decreasing amounts of choles terylpelargonate (CP) were added increasing amounts Table 11 Wt. CIC Wt. 71 CP Temp. (C.) Start Of Red Blue Compared to a liquid crystalline system consisting of a series of compositions comprising cholesteryl oleyl carbonate (COC) and cholesteryl pelargonate (CP) the above CIC and CP system on a weight per cent basis, is approximately 2 C. higher but is more fluid throughout .the entire range without degrading optical properties.

EXAMPLE 111 Both an /20 by weight per cent composition of cholesteryl pelargonate (CP)/cholesteryl oleyl carbonate (COC) and an 80/20 by weight per cent composition of cholesteryl pelargonate (CP)/cholesteryl isostearyl carbonate (CIC), after heated to an isotropic melt, were subjected to a temperature of 5 C.. Samples were periodically tested to determine a composition 50- lidification point. The CP/COC composition solidified in about 3%hours, whereas the CP/CIC composition was still fluid indicating solidification retardation due to the isostearyl fraction of the CIC molecule. Other CP/COC to CP/CIC ratios yielded the same result, that is, CIC containing compositions were still fluid whereas COC containing compositions were solid.

EXAMPLE IV An 80/20 by weight per cent composition of cholesteryl pelargonate (CP)/sitosteryl oleyl carbonate (SOC) and an 80/20 by weight per cent composition of cholesteryl pelargonate (CP)/sitosteryl isostearyl car- 'bonate (SIC), after heated to an isotropic melt, were subjected to a temperature of 5 C.. Samples were periodically tested to determine a composition solidification point. The CP/SOC composition solidified in about three-fourths hour whereas the CP/SIC composition was still fluid indicating solidification retardation due to the isostearyl of the SIC molecule.

EXAMPLE V Table III Wt. "/1 CP Wt. /2 SIC Temp. (C.) Start Of Red Green Blue 90.0 10.0 59.0 60.0 61.0 80.0 20.0 46.0 47.5 49.0 70.0 30.0 41.0 41.5 43.0 50.0 50.0 Nothing Unlike cholesteryl isostearyl carbonate (CIC), SIC exhibits no detectable visible color play, however it can be used in combinations with other liquid crystalline materials to retard solidification without degrading optical properties of the various compositions.

EXAMPLE VI To compositions of decreasing amounts of cholesteryl pelargonate (CP) were added increasing amounts from 10.0 to 50.0 weight per cent of stigmasteryl isostearyl carbonate (StIC). These compositions were melted together and coated onto a black coated temperature probe to a thickness of about four thousandths of an inch. Color was read perpendicular to the surface with the light also normal to the surface of the liquid crystalline film.

Table IV presents examples that illustrate the use of StlC with CP, a typical liquid crystalline material, and the resulting color play temperature range.

Table IV Wt. CP Wt. '71 StlC Temp. (C.) Start Of Red Green Blue 90.0 l0.0 63.0 64.0 65.0 80.0 20.0 55.5 56.5 57.5 70.0 30.0 50.0 51.5 53.0 50.0 50.0 (Faint blue blush 4045 C.)

EXAMPLE VII To 48.5 parts of cholesteryl isostearyl carbonate (CIC), 44.9 parts cholesteryl pelargonate (CP), and 1.8 parts cholesteryl chloride (CCl) was added 4.8 parts p-(p'-ethoxy phenyl azo) phenyl hexanoate. All components were added by weight per cent. The spectrum produced by this composition displayed an enhanced brillanee which was attributed to the addition of the nematic liquid crystalline material, p-(p'-ethoxy phenyl azo) phenyl hexanoate. This nematic reduced the viscosity of the composition and synergistically with CIC prevented solidification for much longer periods of time, and at lower storage temperatures than has heretofore been possible, and further stabilized liquid crystalline compositions when they were exposed to aging, temperature, oxygen, ultraviolet, or sunlight tests.

EXAMPLE VIll To 40.0 parts of cholesteryl pelargonate (CP) and 40.0 parts cholesteryl isostearyl carbonate (CIC) was added 20.0 parts cholesteryl 2-ethyl hexyl carbonate (CEHC). All components were added by weight per cent. These materials were heated to produce an isotropic melt which was coated onto a black coated temperature probe to a thickness of about one to four thousandths of an inch. Color was read perpendicular to the surface with the light also normal to the surface of the film. The composition exhibited a brillant color display with start of red at about 10 C. and start of blue at about 17 C.. CEHC has no visible color play range when subjected to temperatures of -1 C. to +l 00 C.. The material became a clear glass between C. and l0 C.. CEHC reduced the viscosity of the composition and synergistically in combination with ClC prevented solidification for even longer periods of time, and at lower storage temperatures than has heretofore been possible with similar compositions containing no CIC.

EXAMPLE [X A composition of equal parts by weight of cholesteryl pelargonate (CP) and cholesteryl isostearyl carbonate (CIC) was microencapsulated according to the teachings disclosed in US. Pat. No. 2,800,457, issued July 23,1957, on the application of Barrett K. Green and Lowell Sehleicher. The resultant microencapsulated liquid crystalline composition was mixed on an equal weight basis with a 10 per cent by weight aqueous solution of polyvinyl alcohol (PVA). The PVA used is about 87 to 89 per cent hydrolyzed, and is characterized by exhibiting a viscosity of about 35 to 45 centipoises in a 4 per cent by weight, aqueous solution at 20 C. (such as material designated by the trademark, Elvanol 50-42" sold by E. I. duPont de Nemours and Co., Wilmington, Del.). The resulting slurry was coated onto (a) black construction paper, and (b) polyester film.

The coated black paper, when subjected to a gradually increasingtemperature, exhibited a brilliant color display with start of red at about 35 C. and start of blue at about 36 Co.

The PVA/liquid crystalline composition coating was stripped from the polyester film and coated with a black paint. The resultant matrix exhibited a color play range substantially identical to the coating on black construction paper.

EXAMPLE x Twenty grams of a 65/35 by weight composition of cholesteryl isostearyl carbonate (ClC)/cholesteryl pelargonate (CP), heated until it was an isotropic melt, was emulsified into 100 grams of a 10 per cent by weight aqueous solution of polyvinyl alcohol (PVA, such as Elvanol 50-42). The emulsion was coated at ambient temperature onto a black glass substrate. The resultant liquid crystalline composition embedded in a PVA matrix exhibited a color play range with start of red at about 280 C. and start of blue at about 28.5 C..

In view of the teachings and examples, it is apparent that the effects and advantages of the invention, especially retardation of solidification of liquid crystalline compositions for an extended period of time, can be obtained by preparing and incorporating effective amounts of compounds which are steroid derivatives of isostearyl carbonate.

Although the foregoing teachings and examples relate to cholesteryl isostearyl carbonate, sitosteryl isostearyl carbonate and stigmasteryl isostearyl carbonate, it will be possible to prepare and obtain results substantially similar with other compounds closely related in structure and properties. For example, it is apparent that the carbon 5 carbon 6 position of the cyclopentenophenanthrene ring system may be saturated with hydrogen and/or halogen to yield cholestanol, halocholestanol, sitostanol, halositostanol, stigmastanol or halostigmastanol, and the corresponding isostearyl carbonates made from these compounds may be expected to exhibit similar solidification retardation effects.

Thus it is apparent that the invention affords a new class of cholesteric-phase and nematic-phase liquid crystalline solidification retarded compositions that will find use in such applications as thermal-pattern sensing devices, vapor-detecting devices, rate of shear sensing devices, electronic sensing devices, magnetic sensing devices and the like.

While we have shown and described herein certain embodiments of our invention, we intend to cover as well any change or modification therein which may be made without departing from its spirit and scope.

We claim as our invention:

1. A cholesteric liquid crystalline composition containing about lO- weight per cent of a compound for use in retarding crystallization the cholesteric of liquid crystalline material, said compound having the formula wherein Ris a derivative of asteroid group selected from the group consisting of cholesterol, stigmasterol and sitosterol; and where the chemical bond linkage of carbon to carbon 6 of said steroid group is selected from a group consisting of X being a halogen.

2. A composition as defined in claim 1, characterized I in that said'compound is cholesteryl isostearyl carbonate Q 3. A composition as defined in claim 1, characterized in that said composiition is embedded in a matrix of wherein R is a derivative of a steroid group selected from the group consisting of cholesterol, stigmasterol and sitosterol; and where the chemical bond linkage of carbon 5 to carbon 6 of said steroid group is selected from a group consisting of lighttransmitting polymeric material. that said composition is embedded 4. A composition as defined in claim 1, characterized in that said composition is microencapsulated.

X being a halogen.

7. The stratum as defined in claim 6, characterized in that said crystallization retarding compound is cholesteryl isostearyl carbonate. 

1. A CHOLESTERIC LIQUID CRYSTALLINE COMPOSITION CONTAINING ABOUT 10-80 WEIGHT PER CENT OF A COMPOUND FOR USE IN RETARDING CYRSTALLIZATION THE CHOLEXTERIC OF LIQUID CRYSTALLINE MATERIAL, SAID COMPOUND HAVING THE FORMULA
 2. A composition as defined in claim 1, characterized in that said compound is cholesteryl isostearyl carbonate.
 3. A composition as defined in claim 1, characterized in that said composiition is embedded in a matrix of light-transmitting polymeric material. that said composition is embedded
 4. A composition as defined in claim 1, characterized in that said composition is microencapsulated.
 5. A composition as defined in claim 4, characterized in that said microencapsulated composition is embedded in a matrix of light-transmitting polymeric material.
 6. In stratum about 1-50 microns thick of a cholesteric liquid crystalline composition, the improvement wherein said composition contains about 10-80 weight per cent of a crystallization retarding compound having the formula
 7. The stratum as defined in claim 6, characterized in that said crystallization retarding compound is cholesteryl isostearyl carbonate. 